01312nas a2200181 4500008004100000245010100041210006900142260000800211300001400219490000700233520065000240100002600890700002900916700002200945700002400967700002200991856011701013 2016 eng d00aSelective synthesis of N-unsubstituted and N-arylindoles by the reaction of arynes with azirines0 aSelective synthesis of Nunsubstituted and Narylindoles by the re cSEP a8604-86110 v813 a

The transition-metal-free and temperature-dependent highly selective reaction of arynes with 2H-azirines allowing the synthesis of either N-unsubstituted or N-arylindoles has been developed. At 60 degrees C, arynes generated from 2-(trimethylsilyl)aryl triflates smoothly insert into 2H-azirines to form 2,3-diarylindoles with high selectivity. Interestingly, when the reaction was performed at -10 degrees C, the selectivity was switched to the formation of 1,2,3-triarylindoles in good yields.

1 aThangaraj, Manikandan1 aBhojgude, Sachin, Suresh1 aJain, Shailja", "1 aGonnade, Rajesh, G.1 aBiju, Akkattu, T. uhttp://library.ncl.res.in/content/selective-synthesis-n-unsubstituted-and-n-arylindoles-reaction-arynes-azirines01710nas a2200169 4500008004100000245012800041210006900169260000800238300001600246490000700262520105300269100002901322700001401351700002401365700002201389856012901411 2016 eng d00aSubstrate-controlled selectivity switch in the three-component coupling involving arynes, aromatic tertiary amines, and CO20 aSubstratecontrolled selectivity switch in the threecomponent cou cOCT a5424–54270 v183 a

The transition-metal-free multicomponent coupling involving arynes, aromatic tertiary amines, and CO2 is reported. The reaction exhibits switchable selectivity depending on the electronic nature of the aromatic amines used. With amines bearing electron-releasing/neutral groups as the nucleophilic trigger, the reaction afforded 2-arylamino benzoates via a nitrogen to oxygen alkyl group migration. Employing electron-deficient amines in the reaction furnished 2-aminoaryl benzoates proceeding via the aryl to aryl amino group migration resembling a Smiles rearrangement.

1 aBhojgude, Sachin, Suresh1 aRoy, Tony1 aGonnade, Rajesh, G.1 aBiju, Akkattu, T. uhttp://library.ncl.res.in/content/substrate-controlled-selectivity-switch-three-component-coupling-involving-arynes-aromatic